JP2006272131A - Method and apparatus for reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable stabilization of a reaction in the initiation and during proceeding of the reaction because even a gas-generating reaction system can be mixed uniformly and efficiently without disturbance of bubbles of the gas and stable liquid feeding to subsequent processes. <P>SOLUTION: A reaction method for a reaction system generating a gas during the reaction comprises mixing two or more solutions L1 and L2 in a tightly closed mixer 12 and feeding the mixed solution to a degassing unit 14 having a gas-liquid interface 84 to remove continuously bubbles 98 of the gas produced in the reaction from the reaction solution to a space 82. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a reaction method and apparatus, and more particularly to a reaction method and apparatus in a reaction system in which gas bubbles are generated in a liquid-liquid reaction.

  When handling a reaction system in which gas bubbles are generated in a liquid-liquid reaction, in order to stabilize the reaction at the start of the reaction and in the course of the reaction, the bubbles are actively removed in both the batch process and the continuous flow process. Need to degas. In the case of a batch process, if mixing is performed with a stirrer in a system in which bubbles are mixed, shearing force is less likely to be applied to the continuous phase due to fluctuations in the volume of the bubbles, so that stirring efficiency is reduced and uniform mixing cannot be performed. Also, in the case of continuous flow process, if bubbles are mixed, the flow of continuous processing becomes unstable, the mixing field and reaction field become non-uniform, and the reaction equilibrium does not easily advance to the reaction promoting side. And liquid feeding to the subsequent process becomes unstable.

  An example of a reaction system that generates a gas is the production of magnetic particles contained in a magnetic layer of a magnetic recording medium. In order to produce magnetic particles having a small particle size and excellent monodispersibility, the liquids that initiate the reaction for forming the metal fine particles must be uniformly and efficiently mixed, and are generated by the reaction. It is necessary to remove quickly so that gas (for example, hydrogen gas) does not disturb mixing.

As a conventional reaction apparatus having a degassing function, there is Patent Document 1, in which a mixing stirrer is provided at a lower part in a reaction tank for performing a chemical reaction, and a defoaming blade is provided at an upper part in the reaction tank. It is disclosed that the bubbles of gas floating in the liquid are mechanically defoamed by breaking the bubbles of the gas with the shearing force of the defoaming blade.
JP-A-9-10507

  However, in the case of Patent Document 1, the mixing reaction operation and the degassing operation in the stirrer proceed simultaneously in the reaction tank, and bubbles are accumulated in the reaction tank. The bubbles interfere with the mixing of each other, and the stirring efficiency decreases. Due to the decrease in the stirring efficiency, the mixing for starting the reaction is not uniformly performed, so that the reaction at the start of the reaction and the reaction progressing process becomes unstable.

  The present invention has been made in view of such circumstances, and even in a reaction system in which gas is generated with the reaction, mixing can be performed uniformly and efficiently without being obstructed by gas bubbles. An object of the present invention is to provide a reaction method and apparatus capable of stabilizing the reaction at the start and in the course of the reaction, and capable of performing stable liquid feeding to the subsequent process.

  According to a first aspect of the present invention, in order to achieve the above object, in a reaction method of a reaction system in which gas is generated along with the reaction, a mixture is mixed with a closed system mixing unit that starts reaction by mixing a plurality of liquids. Separating the gas bubbles generated from the reaction liquid from the degassing part having a gas-liquid interface for removing the gas bubbles from the reaction liquid, and sending the reaction liquid mixed in the mixing part to the degassing part. A featured reaction method is provided.

  According to claim 1 of the present invention, a mixing section for mixing a plurality of liquids to start a reaction, and a gas-liquid interface for removing gas bubbles generated when the reaction is started by mixing from the reaction liquid Since the reaction liquid mixed in the mixing section is sent to the degassing section, the mixing is performed uniformly and efficiently without being obstructed by gas bubbles generated by the reaction. Can be done. Thereby, the reaction at the start of the reaction can be stabilized. In addition, gas bubbles generated with the progress of the reaction are efficiently degassed from the gas-liquid interface in the degassing section, so that the reaction in the course of the reaction can be stabilized and degassed by degassing. Since the flow of the reaction liquid in the part is stabilized, stable liquid feeding can be performed to the subsequent process.

  Here, it is the time for sending the reaction liquid from the mixing section to the degassing section, but it is preferable to select the method according to the reaction rate to be handled. For example, when gas bubbles are generated immediately after completion of mixing at a high reaction rate, the reaction solution is preferably sent immediately to the degassing section within 0.1 to 5 seconds after the completion of mixing. More preferably, it is within 3 seconds.

  In addition, the reaction method of the present invention may be used in a batch system in which the liquid charged in the mixing unit is batch-mixed and all of the reaction liquid mixed in the mixing unit is charged into the degassing unit when mixing is completed, or You may prepare the tank etc. which store a liquid, and may use for the continuous flow system which flows continuously from the tank in order of a mixing part and a degassing part.

  A second aspect of the present invention according to the first aspect is characterized in that the mixing unit performs instantaneous mixing.

  This is because if the time from the start of mixing to the end of mixing is long in the mixing section, there is a problem that the gas generated in the latter half of the mixing lowers the mixing efficiency, but there is no such problem if instantaneous mixing is performed.

  A third aspect of the present invention is the passage according to the first or second aspect, wherein the degassing part is a passage that forms the gas-liquid interface by a liquid part by the reaction liquid and a space part in which the gas removed from the reaction liquid is accumulated. Gas bubbles in the reaction solution flowing through the passage are removed in the space.

  Since the degassing part is configured as a passage having a gas-liquid interface between the liquid part by the reaction liquid and the space part in which the gas removed from the reaction liquid accumulates, the gas generated as the reaction proceeds Bubbles can be efficiently removed from the gas-liquid interface into the space. Moreover, since the passage length for degassing can be ensured long by using the passage, bubbles in the reaction solution can be reliably removed.

  A fourth aspect is characterized in that, in the third aspect, the pressure in the space is reduced.

  Thus, by reducing the pressure in the space part, gas bubbles in the reaction solution can easily escape to the space part.

  A fifth aspect of the present invention is the method according to the third or fourth aspect, wherein the passage has an ascending passage and a descending passage through which the reaction solution continuously flows, and the gas-liquid is disposed at a portion where the flow is reversed from the ascending passage to the descending passage. An interface is formed.

  According to the fifth aspect, since the gas-liquid interface is formed in the portion where the flow of the reaction liquid is reversed from the ascending passage to the descending passage, the bubbles rising together with the reaction solution in the ascending passage stay at the gas-liquid interface, and the reaction Only the liquid descends the descending passage. Bubbles staying at the gas-liquid interface are gradually broken and collected as gas in the space. In this way, by providing the reaction liquid ascending passage in the passage, both the buoyancy of the bubbles and the ascent of the reaction liquid can be used, so that the bubbles can be more effectively levitated and separated. .

  A sixth aspect of the present invention is characterized in that, in any one of the third to fifth aspects, the reaction solution flows through a passage in which the ascending passage and the descending passage are configured in multiple stages.

  Since the reaction liquid proceeds while flowing in the passage and gas bubbles are generated, the ascending passage and the descending passage are configured in multiple stages, so that the reaction of the reaction liquid is completed until the reaction of the reaction liquid is completed. Bubbles can be effectively degassed.

  A seventh aspect of the present invention is characterized in that, in any one of the first to sixth aspects, the reaction temperature is controlled by heating or cooling the reaction liquid flowing through the degassing section.

  By controlling the reaction temperature by heating or cooling the reaction liquid flowing through the degassing section, the reaction conditions can be kept constant regardless of the temperature and room temperature, so the amount of gas generated is not affected by the temperature. Can be kept constant. This makes it possible to perform degassing with high accuracy and accurately reproduce the degassing amount in the designed degassing device regardless of the season and room temperature. Can be fixed.

  An eighth aspect is characterized in that in any one of the first to seventh aspects, an ultrasonic wave is applied to the reaction liquid flowing through the degassing section.

  Bubbles attached to the wall of the passage are not easily degassed, but the bubbles attached to the wall are more easily peeled off by applying ultrasonic waves to the reaction liquid flowing through the degassing part and vibrating the reaction liquid. Bubbles can be degassed.

  A ninth aspect of the present invention is characterized in that, in any one of the fifth to eighth aspects, the flow rate of the reaction liquid flowing through the descending passage is slower than the rising speed of the bubbles.

  Gas bubbles are also generated in the reaction liquid flowing through the descending passage, but in the descending passage, the buoyancy of the bubbles and the flow of the reaction liquid are reversed, and the bubbles are less likely to float and separate at the gas-liquid interface. Therefore, if the flow rate of the reaction liquid flowing in the descending passage is made slower than the rising speed of the bubbles, the bubbles can be efficiently levitated and separated also in the descending passage.

  A tenth aspect of the present invention is characterized in that, in any one of the first to ninth aspects, the inside of the degassing part can be seen through.

  Since the inside of the degassing part can be seen through, the degassing state can be accurately grasped.

  According to an eleventh aspect of the present invention, in order to achieve the above object, in a reaction system reaction apparatus that generates a gas in response to a reaction, a sealed system mixing unit that starts reaction by mixing a plurality of liquids, and the mixing And a degassing part having a gas-liquid interface for removing gas bubbles generated from the reaction liquid mixed in the mixing part from the reaction liquid. The reaction apparatus characterized by this is provided.

  In the eleventh aspect of the present invention, the present invention is configured as an apparatus, and mixing can be performed uniformly without being obstructed by gas bubbles generated by the reaction. Can be stabilized, and stable liquid feeding can be performed to the subsequent process.

  In a twelfth aspect of the invention according to the eleventh aspect, the mixing unit supplies at least one of the plurality of liquids by a high-pressure jet flow of 1 MPa or more to a mixing chamber having a residence time of 5 seconds or less and instantaneously mixes with other liquids. It is a high-pressure mixing device for mixing.

  Claim 12 is a preferred means for achieving instantaneous mixing in the mixing section, wherein at least one liquid of a plurality of liquids is supplied in a high-pressure jet flow of 1 MPa or more to a mixing chamber having a residence time of 5 seconds or less. A high-pressure mixing device that instantaneously mixes with another liquid is preferable.

  A thirteenth aspect of the present invention is the passage according to the eleventh or twelfth aspect, wherein the degassing part is a passage that forms the gas-liquid interface by a liquid part by the reaction liquid and a space part in which gas removed from the reaction liquid is accumulated A degassing vessel having an inlet and an outlet for the reaction solution, a plurality of dam plates standing from the bottom of the degassing vessel and having an upper end located below the gas-liquid interface, and between the dam plates And an upper end is located above the gas-liquid interface and a lower end is configured with a baffle plate spaced from the bottom of the degassing container, and the reaction liquid is continuously contained in the degassing container. A rising passage and a descending passage are formed, and the gas-liquid interface is formed at a portion where the flow is reversed from the ascending passage to the descending passage.

  A thirteenth aspect of the present invention shows a preferred embodiment in which the degassing part is configured as a passage having a gas-liquid interface between the reaction liquid and the space part. As described above, the degassing container includes a barrier plate and a baffle plate. It constitutes a passage.

  A fourteenth aspect is the one according to the thirteenth aspect, wherein the space portion is not partitioned by the baffle plate.

  Thus, the pressure of the whole space part can be equalized by not partitioning a space part with a baffle plate. In this case, a baffle plate may not be provided in a portion corresponding to the space portion, or a communication hole may be formed in a portion corresponding to the space portion of the baffle plate.

  A fifteenth aspect is characterized in that, in the thirteenth or fourteenth aspect, the height of the dam plate is low from the inlet to the outlet of the degassing container.

  This is because in the passage formed in the degassing vessel, the gas generation amount from the reaction liquid is larger as it is closer to the inlet side, and the gas generation amount is smaller toward the outlet side. For this reason, it is necessary to ensure a longer passage length to the gas-liquid interface on the inlet side of the passage. Therefore, if the height of the weir plate is lowered as it goes from the inlet to the outlet of the degassing vessel, the passage length to the gas-liquid interface can be formed according to the amount of gas generated, and it is necessary to unnecessarily increase the passage length. Absent.

  A sixteenth aspect is characterized in that in any one of the thirteenth to fifteenth aspects, a pressure adjusting means for adjusting the pressure of the space portion is provided.

  By adjusting the pressure in the space by the pressure adjusting means, it is possible to form a space pressure in which bubbles can easily escape from the reaction solution flowing through the passage.

  A seventeenth aspect is characterized in that in any one of the eleventh to sixteenth aspects, the degassing part is provided with a temperature adjusting means for controlling the reaction temperature by heating or cooling the reaction liquid.

  By controlling the reaction temperature by heating or cooling the reaction liquid flowing through the degassing section, the reaction conditions can be kept constant regardless of the temperature and room temperature, so the amount of gas generated is not affected by the temperature. Can be kept constant. This makes it possible to perform degassing with high accuracy and accurately reproduce the degassing amount in the designed degassing device regardless of the season and room temperature. Can be fixed.

  An eighteenth aspect is characterized in that, in any one of the eleventh to seventeenth aspects, the degassing part is provided with an ultrasonic wave applying means for applying an ultrasonic wave to the reaction liquid.

  Degassing efficiency can be improved by irradiating the reaction liquid flowing through the passage with ultrasonic waves.

  A nineteenth aspect of the present invention is characterized in that, in any one of the thirteenth to eighteenth aspects, a stirrer that forms a flow that prevents stagnation is provided at the bottom of the rising passage formed in the degassing vessel.

  For example, when metal fine particles are produced by a reaction, such as in the production of magnetic particles, the metal fine particles easily settle on the bottom of the degassing vessel, but a stirrer that forms a flow that prevents stagnation at the bottom of the ascending passage is provided. By providing, it can be made difficult to settle.

  A twentieth aspect according to any one of the thirteenth to nineteenth aspects is characterized in that a cross-sectional area of the descending passage with respect to the ascending passage is made different.

  For example, if the flow rate of the reaction liquid flowing through the passage is set to be slower in the descending passage than in the ascending passage, bubbles generated in the descending passage are also easily floated and separated at the gas-liquid interface.

  A twenty-first aspect of the present invention is the method according to any one of the thirteenth to twentieth aspects, wherein the inner surface of the degassing vessel, the surface of the barrier plate, and the surface of the baffle plate are subjected to a surface treatment that prevents the gas bubbles from adhering. It is characterized by being.

  Since surface treatment that prevents gas bubbles from adhering to the inner surface of the degassing container, the surface of the weir plate, and the surface of the baffle plate has been performed, the bubbles are less likely to adhere and are easily degassed.

  A twenty-second aspect of the present invention is characterized in that, in any one of the thirteenth to twenty-first aspects, a bottom shape of a degassing container in which the flow of the reaction liquid is reversed from the descending passage to the ascending passage is formed in an arc shape.

  Since the bottom shape of the degassing vessel that reverses from the descending passage to the ascending passage is formed in an arc shape, the reaction solution flows smoothly in the passage, and even when fine particles are generated by the reaction as described above, the bottom of the container Therefore, it is difficult to deposit fine particles.

  A twenty-third aspect is characterized in that, in any one of the thirteenth to twenty-second aspects, the reaction by the plurality of liquids is a reaction for generating magnetic particles.

  Claims 24 and 25 are magnetic particles produced by the reaction method and apparatus of the present invention, and Claim 26 is a magnetic recording medium containing the magnetic particles in a magnetic layer.

  As described above, according to the reaction method and apparatus of the present invention, the mixing can be performed uniformly and efficiently without being obstructed by the gas bubbles generated during the reaction. The reaction in the process can be stabilized and the liquid can be stably fed to the subsequent process. Therefore, if the present invention is applied to the production of magnetic particles, magnetic particles having a small particle size and excellent monodispersibility can be produced.

  Hereinafter, preferred embodiments of a reaction method and apparatus according to the present invention will be described with reference to the accompanying drawings.

  FIG. 1 is an overall configuration diagram of the reaction apparatus of the present invention, which is an example of a continuous flow system. The reaction apparatus 10 of the present invention can be applied to any reaction system in a liquid phase reaction method (liquid-liquid reaction) as long as it is a reaction that continuously generates gas as the reaction proceeds. In the embodiment, an example applied to continuous production of metal fine particles contained in a magnetic layer of a magnetic recording medium will be described below. Further, an example of a solution in which a solute that generates metal fine particles is dissolved in a solvent as a liquid will be described.

  As shown in FIG. 1, the reaction apparatus 10 is mainly provided with a closed mixing apparatus 12 that starts a reaction by mixing a plurality of solutions, and the mixing apparatus 12 separated from each other. And a degassing device 14 having a gas-liquid interface that removes gas bubbles generated from the reaction solution LM mixed in the reaction solution LM.

  As the first solution L1 for producing metal fine particles, a reducing agent solution can be suitably used. As the second solution L2, a solution containing two or more kinds of metal ions selected from groups 8, 9, and 10 of the periodic table can be suitably used. Fe, Pt, Co, Ni, Pd can be used. Metal ions are preferred.

Of the liquid phase reaction methods, the reverse micelle method is preferred, in which the particle size of the metal fine particles can be easily controlled, and the first and second solutions L1 and L2 are reversed using a water-insoluble organic solvent containing a surfactant. It is preferable to prepare it as a micelle solution. An oil-soluble surfactant is used as the surfactant to be used. Specifically, sulfonate type (for example, aerosol OT (manufactured by Wako Pure Chemical Industries), quaternary ammonium salt type (for example, cetyltrimethylammonium bromide), ether type (for example, pentaethylene glycol dodecyl ether) and the like can be mentioned. Further, preferable examples of the water-insoluble organic solvent for dissolving the surfactant include alkanes, ethers, alcohols, etc. The alkanes are preferably alkanes having 7 to 12 carbon atoms. Is preferably heptane, octane, isooctane, nonane, decane, undecane, dodecane, etc. The ether is preferably diethyl ether, dipropyl ether, dibutyl ether, etc. The alcohol is preferably ethoxyethanol, ethoxypropanol, or the like. , Reducing agent solution The reducing agent, alcohols, _{polyalcohols; H 2; HCHO, S 2} O 6 2-, BH 4 -, + N 2 H 5, H 2 PO 3 - be used alone compounds containing such However, it is preferable to use two or more kinds in combination.

  The first solution L1 and the second solution L2 are separately prepared in the first preparation tank 16 and the second preparation tank 18 disposed in the vicinity of the mixing device 12. That is, in the first preparation tank 16, a water-insoluble organic solvent containing a surfactant and a reducing agent aqueous solution are mixed by a stirrer 16a to prepare a reverse micelle solution of the first solution L1. In the second preparation tank 18, a water-insoluble organic solvent containing a surfactant and a metal salt aqueous solution containing two or more kinds of metal ions selected from Groups 8, 9, and 10 of the periodic table are mixed with a stirrer 18a. A reverse micelle solution of the second solution L2 is prepared by mixing. In addition, heating jackets 20 and 20 are provided on the outer peripheries of the first preparation tank 16 and the second preparation tank 18, respectively, and are heated to an appropriate temperature at which an initial reaction is performed.

  The first and second solutions L1 and L2 prepared in the first and second preparation tanks 16 and 18 are supplied to the mixing device 12 by the supply pumps 26 and 28 via the supply pipes 22 and 24, respectively. Is done. In the mixing device 12, the two solutions L 1 and L 2 are instantaneously mixed and discharged from the mixing device 12, and flow through the pipe 30 and are sent to the degassing device 14. The reaction is started by the mixing device 12, and gas is continuously generated as the reaction proceeds. The reaction liquid LM that has started the reaction in the mixing device 12 proceeds in the degassing device 14 and the generated gas is continuously and efficiently degassed. The reaction liquid LM that has passed for a fixed time in the degassing device 14 is sent to the product tank 34 via the pipe 32. A heating / cooling jacket 36 is provided on the outer periphery of the product tank 34, and the liquid temperature is heated or cooled as necessary.

  A reaction system that generates gas by a chemical reaction can efficiently and uniformly mix the first and second solutions L1 and L2 without interfering with mixing by the generated gas, and further, continuously as the reaction proceeds. It is important how efficiently the generated gas can be degassed.

  According to the present invention, a sealed mixing device 12 for mixing a plurality of solutions L1 and L2 to start a reaction, and a gas for removing gas bubbles generated when the reaction is started by mixing from the reaction solution LM. Since the degassing device 14 having a liquid interface is separated and the reaction liquid LM mixed by the mixing device 12 is sent to the degassing device 14, the mixing device 12 generates gas bubbles generated by the reaction. Mixing can be performed uniformly and efficiently without obstruction. Thereby, since the mixing efficiency can be increased, unreacted substances can be eliminated, the yield of metal fine particles can be increased, and the reaction at the start of the reaction can be stabilized. In addition, since the gas bubbles generated as the reaction progresses are continuously and efficiently degassed in the degassing device 14, the reaction in the course of the reaction can be stabilized and continuously degassed. As a result, the flow of the reaction liquid LM in the degassing device 14 is stabilized, so that stable liquid feeding can be performed to the subsequent process.

  In addition, although the reaction apparatus 10 in this invention may be a batch system or a flow system, it is preferable to select a system according to the reaction rate handled. For example, when the reaction rate is fast and gas bubbles are generated immediately after the end of mixing, the time from the end of mixing to the start of degassing can be made as short as possible by directly connecting the mixing device 12 and the degassing device 14. preferable. Further, when the reaction rate is high, it is preferable to directly connect the mixing device 12 and the degassing device 14 and adopt the flow method for both the mixing device 12 and the degassing device 14. The time from the completion of mixing by the mixing device 12 to the start of degassing by the degassing device is preferably about 0.1 to 5 seconds, more preferably about 0.1 to 3 seconds.

  Hereinafter, the preferable aspect of the mixing apparatus 12 and the degassing apparatus 14 in this invention is demonstrated.

(A) Mixing device The mixing device 12 is preferably of a type that can instantaneously mix and immediately discharge the mixed reaction liquid LM. For example, a high-pressure mixing method can be suitably used. In the following, three types of high-pressure mixing systems of one-jet type, T-shaped / Y-shaped, and two-jet opposed type will be described. In addition, as long as instantaneous mixing is possible, not only a high pressure mixing system but any mixing system may be used, for example, a static mixer or the like can be used.

a) One Jet Type FIG. 2 is a cross-sectional view showing the concept of the one jet type mixing device 12.

  As shown in FIG. 2, the mixing device 12 has one end side of a mixer 40 in which a cylindrical mixing chamber 38 (mixing field) in which the first and second solutions L1 and L2 are mixed and reacted is formed. A first conduit 42 for introducing the first solution L1 into the mixing chamber 38 is connected to the opening, and a discharge pipe 44 for the reaction liquid LM that is mixed and reacted in the mixing chamber 38 is connected to the other end side opening. . Further, a second conduit 46 for introducing the second solution L2 into the mixing chamber 38 is connected to the side of the mixer 40 near the outlet of the first conduit 42. A first orifice 48 and a second orifice 50 are formed in the distal ends of the first conduit 42 and the second conduit 46, respectively, thereby disturbing the first conduit 42 and the second conduit 46. A first nozzle 52 and a second nozzle 54 are formed for ejecting a stream of liquid. In FIG. 2, the first solution L1 is introduced from the first conduit 42 and the second solution L2 is introduced from the second conduit 46. However, both solutions can be reversed. Further, if the connection position of the discharge pipe 44 is in the vicinity of the other end side of the mixer 40, the discharge pipe 44 may be connected to the side surface portion of the mixer 40.

  A jacket 56 through which a heat medium having a relatively large heat capacity such as water or oil flows is wound around the outer periphery of the mixer 40, and a heat medium inlet 56A and a heat medium outlet 56B of the jacket are not shown. Connected to the supply device. The mixing reaction temperature is preferably set appropriately to a predetermined temperature suitable for the initial reaction depending on the types of the first and second solutions L1 and L2.

  In addition, when preparing the 1st solution L1 by the number of multiple types of metal atoms, and mixing these multiple solutions and the 2nd solution L2, one of these solutions is a high-pressure jet of 1 MPa or more. Just flow. Therefore, a plurality of nozzle positions for ejecting the plurality of first solutions L1 may be provided on the side surface side of the mixer 40, or the plurality of first solutions L1 may be ejected in order from one nozzle position. Good. Accordingly, the number of nozzles of the straight flow high-pressure jet flow is basically one, but there may be a plurality of nozzles of cross flow orthogonal to the straight flow.

  As a method of drilling the first and second orifices 48 and 50 in the block-shaped orifice material 58, as a processing method of precisely opening an ejection hole of about 100 μm in the orifice material 58 of metal, ceramics, glass or the like. Known micro cutting processing, micro grinding processing, injection processing, micro electric discharge processing, LIGA method, laser processing, SPM processing and the like can be suitably used.

  The material of the orifice material 58 is preferably a material having good workability and a hardness close to diamond. Therefore, as materials other than diamond, those obtained by hardening various metals and metal alloys such as quenching, nitriding, and sintering can be preferably used. Ceramics can also be suitably used because of its high hardness and superior workability than diamond. In the present embodiment, an example of an orifice will be described as the throttle structure of the first nozzle 52 and the second nozzle 54. However, the orifice structure is not limited to the orifice as long as it has a function of ejecting turbulent liquid. Other methods can be used.

  The first conduit 42 and the second conduit 46 are provided with pressurizing means (not shown), and the first solution L1 and the second solution L2 are applied to the first and second nozzles 52 and 54, respectively. Pressure supplied. However, the pressure ejected from the second nozzle 54 to the mixing chamber 38 is made smaller than the pressure of the high-pressure jet stream ejected from the first nozzle 52 to the mixing chamber 38. Various means are known as pressurizing means for applying a high pressure to the liquid, and any means can be used. However, relatively easy and inexpensive means such as a plunger pump and a booster pump are available. It is preferable to use a reciprocating pump. In addition, although a high pressure cannot be generated as much as a reciprocating pump, some rotary pumps can generate a high pressure, and such a pump can be used.

  The first solution L1 is ejected from the first nozzle 52 to the mixing chamber 38 as a turbulent flow having a high pressure jet flow of 1 MPa or more and flowing into the mixing chamber 38 with a Reynolds number of 10,000 or more. The second solution L2 having a pressure lower than that of the first solution L1 is ejected from the mixing chamber 38 as an orthogonal flow substantially orthogonal to the first solution L1. In this case, even if the second solution L2 is not completely orthogonal to the first solution L1 at an angle of 90 °, the second solution L2 only needs to have an orthogonal velocity vector component as a main component. Thus, the first solution L1 and the second solution L2 are instantaneously and efficiently mixed under an appropriate mixing reaction temperature condition, and the reacted reaction solution LM is immediately discharged from the discharge pipe 44. In this case, the residence time in the mixing chamber 38 is preferably 5 seconds or less. As a result, fine metal particles having a fine size and good monodispersibility are formed.

  As schematically shown in FIG. 3, the mixing reaction is performed by the second solution ejected from the substantially orthogonal direction with respect to the first solution L <b> 1 to the first solution L <b> 1 having a high-speed turbulent high-pressure jet flow. By entraining L2 to entrain, the high vortex viscosity generated by mixing the first solution L1 and the second solution L2 is used to obtain high-performance mixing efficiency. The mixing chamber 38, the first and second nozzles 52 and 54, and the discharge pipe 44 are formed to have the following relationship.

That is, it is necessary to eddy viscosity in the mixing chamber 38 is formed, the cylinder diameter D ₁ of the mixing chamber 38 is the orifice diameter D ₂ of the first nozzle 52, the orifice diameter D ₃ of the second nozzle 54 Formed in large diameter. In particular eddy viscosity making the first solution L1 is a straight flow A is important in improving the mixing efficiency, dimensional ratio of the cylindrical diameter D ₁ of the mixing chamber 38 for the orifice diameter D ₂ of the first nozzle 52 is The range of 1.1 times to 50 times is preferable, and the range of 1.1 times to 20 times is more preferable. Further, in order to make the second solution L2 that is a cross flow B orthogonal to the straight flow A easy to be caught in the solution L1 of the straight flow A, the pressure of the cross flow B is lower than the pressure of the straight flow A. Thus, it is preferable that the jet flow velocity be equal to or less than the jet flow velocity of the straight flow A. Specifically, the flow rate ratio of the jet flow velocity of the cross flow B to the jet flow velocity of the straight flow A is 0.05 to 0.4 times, more preferably 0.1 to 0.3 times.

  Further, the cross flow B is mixed in the mixing chamber 38 at a position before the eddy viscosity C formed by the straight flow A being ejected from the first nozzle 52 having a small diameter into the mixing chamber 38 having a larger diameter is maximized. The second nozzle 54 needs to be disposed between the first nozzle 52 and the maximum position of the eddy viscosity C. Therefore, it is necessary to know the position where the eddy viscosity C is maximized, but the position of the mixing chamber 38 where the eddy viscosity C is maximized is already commercially available in Japan as flow analysis software and is well known as flow analysis software. This can be grasped by performing a simulation in advance using R-Flow, a numerical analysis software manufactured by R-Flow. In this case, as can be seen from FIG. 3, the position where the eddy viscosity C is maximum has a region instead of a pin point, and therefore the maximum position of the eddy viscosity C may be set to a point P that is substantially the center of the eddy viscosity C. . Therefore, the second nozzle 54 may be positioned before the point P, but more preferably the second nozzle 54 is positioned so that the cross flow B can be ejected at an early stage of formation of the eddy viscosity C.

  Further, when analyzed by the above numerical analysis software, the center point P in the region where the eddy viscosity C appears is related to the flow velocity of the straight flow A, and the maximum flow velocity of the straight flow A (usually the flow velocity at the first nozzle position). ) Substantially corresponds to a position where it is reduced to 1/10. Therefore, if the position where the maximum flow velocity of the straight flow A is reduced to 1/10 is calculated and the second nozzle 54 is positioned so that the orthogonal flow B can be ejected before that point, it is also necessary to calculate the point P. Absent.

  In addition, it is necessary to secure the length L (see FIG. 2) of the mixing chamber 38 necessary for forming the maximum eddy viscosity C in the mixing chamber 38, but if the length is too long, the reaction liquid LM is mixed in the mixing chamber 38. Stagnation and backflow are likely to occur, which adversely affects the fine particle size and monodispersity of the metal fine particles. Therefore, the length L of the mixing chamber 38 is preferably 2 to 5 times the distance from the first nozzle 52 to the point P which is the maximum position of the eddy viscosity C, and more preferably 2 to 3 times.

Further, when a liquid is ejected from the first nozzle 52 or the second nozzle 54 with a high-speed flow from the first nozzle 52 or the second nozzle 54 to the larger-diameter mixing chamber 38, cavitation is likely to occur. An interface is formed, reducing the mixing efficiency. Therefore, in order to increase the mixing efficiency by using the eddy viscosity C, it is necessary to prevent the gas-liquid interface from being formed in the mixing chamber 38. Therefore, as shown in FIG. 2, the diameter D ₄ of the discharge pipe 44 is reduced by the third orifice 60 so as to be smaller than the cylinder diameter D _{1 of} the mixing chamber 38, and mixing is performed with the pressure in the mixing chamber 38 raised. is required. Thereby, since cavitation can be eliminated, mixing efficiency is further improved. In addition, in order to shorten the residence time in the portion that does not contribute to mixing in the discharge pipe 44 as much as possible, the outlet in the mixing chamber 38 is throttled and at least a discharge pipe 38 having an inner diameter smaller than the cylinder diameter D ₁ of the mixing chamber 38 is provided. It is good to connect to the piping 30 as short as possible. In this way, by shortening the distance from the mixing device 12 to the degassing device 14, the gas generated by the reaction in the mixing device 12 does not stay in the discharge pipe 44 or the pipe 30, but immediately in the degassing device 14. Degassing can begin.

  Further, the shape of the jet flow ejected from the first nozzle 52 into the mixing chamber 38 is regulated by the first orifice 48 provided in the first nozzle 52, and this jet flow shape affects the mixing performance. Therefore, it is preferable to appropriately use the first orifice 48 that forms a jet flow shape such as a filament shape, a conical shape, a slit shape, or a fan shape in accordance with the purpose of the mixing reaction. For example, in the case of a reaction with a very fast reaction speed on the order of milliseconds, it is necessary to eject the straight flow A and the cross flow B so that the eddy viscosity C is instantaneously maximized in the narrowest possible range. A first orifice 48 that forms a linear jet shape is preferred. Also, when the reaction rate is relatively slow, it is better to increase the entrained interface area created by the straight flow A by jetting the straight flow A and the cross flow B so that the eddy viscosity C is maximized in the widest possible range. In this case, the first orifice 48 which forms a thin jet flow shape is preferable. In the case of an intermediate reaction rate between a very high reaction rate on the order of milliseconds and a relatively low reaction rate, the first orifice 48 that forms a conical jet flow shape is preferable.

  FIGS. 4 to 7 illustrate the first orifice 48 for forming the shape of each of the thread-line shape, the conical shape, the slit shape, and the fan shape, and (a) in each figure shows the orifice at the tip. FIG. 2B is a longitudinal sectional view of the orifice, and FIG. 3C is a transverse sectional view of the orifice.

  FIG. 4 shows a first orifice 48 for ejecting the straight linear flow A in the mixing chamber 38, and is formed in a linear shape. FIG. 5 shows a first orifice 48 for ejecting the conical straight flow A into the mixing chamber 38, which is formed in a trumpet shape having an open front end. FIG. 6 shows the first orifice 48 for ejecting the straight flow A of the thin film into the mixing chamber 38, which is formed in a rectangular slit shape. FIG. 7 shows a first orifice 48 for ejecting a straight flow A of a fan-shaped thin film into the mixing chamber 38, and the tip portion is formed in a fan-like diameter.

  Note that the one-jet mixing type mixing device 12 is not limited to the above-described FIG. 2, and the first solution L1 and the second solution L2 are mixed from the respective nozzles with a diameter larger than the diameter of the nozzles. A high-pressure jet of 1 MPa or more of at least one of the solution L1 and the solution L2 by using a static mixing device that discharges the mixed reaction solution LM from the discharge port smaller than the diameter of the mixing field. In the flow, the reynolds number when flowing into the mixing field is ejected to the mixing field as a turbulent flow of 10,000 or more. Any solution can be used as long as the solution can be added at a pressure lower than that of the high-pressure jet stream.

b) T-shaped / Y-shaped FIG. 8 and FIG. 9 are cross-sectional views of the T-shaped / Y-shaped mixing device 12, FIG. 8 is a T-shaped tube, and FIG. 9 is a Y-shaped tube. .

  As shown in FIGS. 8 and 9, the first solution L1 and the second solution L2 are fed at a pressure of 1 MPa or more at an intersection (mixing field) of very thin pipes such as a T-shaped tube and a Y-shaped tube. The two liquids are mixed instantaneously by colliding with the flow, and the reacted reaction liquid LM is discharged from the discharge pipe in a short time. That is, the first solution L1 is ejected from the first addition pipe 62 to the mixing field 64 with a high-pressure jet flow of 1 MPa or more, and the second solution L2 is ejected from the second addition pipe 66 with a high-pressure jet flow of 1 MPa or more. Both solutions are made to collide by being ejected to the mixing field 64. The reaction liquid LM that has been mixed and reacted by the energy resulting from the collision is discharged from the discharge pipe 68 in a short time. The pressures of the first solution L1 and the second solution L2 may be the same or different as long as the pressure is 1 MPa or more. A jacket 70 is wound around the outer periphery of the first addition pipe 62, the second addition pipe 66, and the discharge pipe 68, and the mixing reaction temperature with the first and second solutions L 1 and L 2 in the mixing field 64. Is controlled. 8 and 9, reference numeral 70A denotes a heat medium inlet of the jacket 70, and reference numeral 70B denotes a heat medium outlet.

  As a result, the first solution L1 and the second solution L2 are reacted instantaneously and efficiently under an appropriate mixing reaction temperature condition, and the reaction solution LM is immediately discharged from the discharge pipe 68. Metal fine particles having a fine size and good monodispersibility can be formed. In this case, the residence time is preferably 5 seconds or less.

c) Two-jet opposed type FIG. 10 shows a mixing method in which the concept of eddy viscosity is added to a T-shape, and the same members as those in FIG. In this mixing method, the first solution L1 and the second solution L2 are mixed in a high-pressure jet flow of 1 MPa or more from the facing direction, and a mixing chamber 38 (mixing) having a diameter larger than the nozzle diameter for ejecting the L1 solution and the L2 solution. The reaction liquid LM is discharged from the discharge pipe 44 having a diameter smaller than the diameter of the mixing chamber 38 by mixing with the eddy viscosity generated in both solutions.

  The mixing device 12 in FIG. 10 has a first solution L1 in an opening on one end side of a mixer 40 in which a cylindrical mixing chamber 38 in which the first solution L1 and the second solution L2 are mixed and reacted is formed. The first conduit 42 for introducing the second solution L2 into the mixing chamber 38 is connected, and the second conduit 46 for introducing the second solution L2 into the mixing chamber 38 is connected to the opening at the other end. A discharge pipe 44 for discharging the reaction liquid LM mixed and reacted in the mixing chamber 38 from the mixing chamber 38 is connected to the central opening of the mixer 40.

A first orifice 48 and a second orifice 50 are provided inside the distal ends of the first conduit 42 and the second conduit 46, respectively, so that the first conduit 42 and the second conduit 46 are not disturbed. A _first nozzle 52 and a second nozzle 54 for injecting straight flow A ₁ and A ₂ are formed. In the present embodiment, an example in which the first solution L1 is ejected from the first nozzle 52 and the second solution L2 is ejected from the second nozzle 54 will be described.

  Further, a jacket 56 is wound around the outer periphery of the mixer 40, and the mixing reaction temperature with the first and second solutions L1 and L2 in the mixer 40 is controlled as described with reference to FIG.

Further, the cylindrical diameter D ₁ of the mixing chamber 38, the orifice diameter D ₂ of the first nozzle 52, the orifice diameter D ₃ of the second nozzle 54, and their dimensional relationship is the same as the one-jet type. Further, the method of forming the first and second orifices 48 and 50, the material of the orifice material 58, and the pressurizing means are the same as described in the one-jet type. Further, the straight flow A ₁ , A ₂ can also be formed in the shape of a thread line, a cone, a slit, or a fan as described in the one-jet type.

11, the one end and the other end of the mixing chamber 38 are fed from the first nozzle 52 and the second nozzle 54 to the first solution L1 and the second solution L2 by a high-pressure jet flow of 1 MPa or more. And collide in the mixing chamber 38 as turbulent straight flow A ₁ and A ₂ facing each other. By overlapping the two eddy viscosities C and D formed by the two straight flow streams A ₁ and A ₂ , the solution L1 and the solution L2 are instantaneously mixed and reacted under an appropriate mixing reaction temperature condition. The liquid LM is immediately discharged from the discharge pipe 44. In this case, the residence time in the mixing chamber 38 is preferably 5 seconds or less. Thereby, fine metal particles having a fine size and good monodispersibility can be formed.

In such a mixing reaction, when the respective eddy viscosities C and D formed in the mixing chamber 38 by the two high-speed straight flow A ₁ and A ₂ of the opposing turbulent flow are maximized, the overlapping portion E is as much as possible. A high-performance mixing efficiency is obtained by overlapping so as to increase. Accordingly, the straight flow A ₁ and A ₂ do not collide with the mixing chamber 38 immediately after being jetted, and the two eddy viscosities C and D formed in the mixing chamber 38 by the straight flow A ₁ and A ₂ overlap. It is preferable to increase the portion E as much as possible. For this purpose, it is preferable to appropriately set the separation distance L (see FIG. 10) between the first nozzle 52 and the second nozzle 54 facing each other, in other words, the length of the mixing field. Thus, by appropriately setting the separation distance L between the first nozzle 52 and the second nozzle 54, it is possible to reliably increase the overlapping portion E between the eddy viscosities C and D that are maximized. In addition, the two eddy viscosities C and D can be substantially completely overlapped. Therefore, it is necessary to know the position where the eddy viscosities C and D are maximized. However, the position of the mixing chamber 38 where the eddy viscosities C and D are maximized is already commercially available in Japan as flow analysis software and is good as flow analysis software. By performing a simulation in advance using a known numerical analysis software, R-Flow, manufactured by R-Flow, the distance from the first nozzle 52 to the eddy viscosity C and the distance from the second nozzle 54 to the eddy viscosity D The distance can be grasped. In this case, as can be seen from FIG. 11, the position where the eddy viscosities C and D are maximum has a region rather than a pinpoint. Accordingly, the separation distance L between the first nozzle 52 and the second nozzle 54 is set to the points P ₁ and P ₂ which are the substantially central portions of the eddy viscosities C and D, and the point P ₁ And the point P ₂ may be set to the total value from the first nozzle 52 to the point P ₁ and the second nozzle 54 to the point P ₂ . As another way to determine the points P _1, P _2, when analyzed by the numerical analysis software, eddy viscosity C caused by rectilinear flow A _1, A _2, points P _1, P ₂ where D is maximized velocity rectilinear flow a _1, a ₂ and is related, the maximum velocity of the rectilinear flow a _1, a ₂ (typically flow velocity in the first or second nozzle position) substantially corresponding to the position decreases 1/10 To do. Accordingly, the points P ₁ and P ₂ may be grasped by calculating the position where the maximum flow velocity of the straight flow A ₁ and A ₂ decreases to 1/10. Thus, by making the eddy viscosities C and D overlap at the position where the eddy viscosities C and D are maximized, the contact efficiency at the liquid-liquid interface between the straight flow A ₁ and the straight flow A ₂ is increased. In addition to the effect of improving the mixing reaction performance, there is also an effect of suppressing heat generation due to liquid-liquid friction caused by the collision of the straight flow A ₁ and the straight flow A ₂ .

(B) Degassing Device The degassing device 14 in the present invention efficiently degass gas bubbles generated as the reaction proceeds from the reaction liquid LM, thereby inhibiting the progress of the reaction and the flow of the reaction liquid LM. Any device can be used as long as it can be avoided, but a degassing device 14 to be described below can be preferably used.

a) Up-and-down meandering flow method The up-and-down meandering-type degassing device 14 shown in FIGS. 12 and 13 is configured so that the liquid part 80 by the reaction liquid LM and the space part 82 in which the gas removed from the reaction liquid LM accumulates. It is formed as a passage 86 having a liquid interface 84. That is, in the degassing container 88 having the inlet 88A and the outlet 88B, a plurality of weir plates 90, 90... Are provided at intervals from the bottom of the degassing container 88, and the upper end of the weir plate 90 is gas-liquid. It is formed so as to be located below the interface 84. A plurality of baffle plates 92 are provided between the barrier plates 90 so as to hang down from the ceiling plate of the degassing container 88, and the lower ends of the baffle plates 92 are separated from the bottom of the degassing container 88. Formed. As a result, as shown in FIG. 13, ascending passages 86 </ b> A and descending passages 86 </ b> B in which the reaction liquid LM continuously flows are formed continuously in the degassing vessel 88 and descend from the ascending passage 86 </ b> A. A gas-liquid interface 84 is formed at a portion where the flow is reversed in the passage 86B. The entire length of the passage 86 composed of the ascending passage 86A and the descending passage 86B needs to be long enough for degassing. An inflow pipe 94 is connected to the inlet 88A of the degassing container 88, and the inflow pipe 94 is connected to the pipe 30 (see FIG. 1) via a flange. On the other hand, an outlet pipe 96 is connected to the outlet 88B of the degassing container 88, and the outlet pipe 96 is connected to the pipe 32 (see FIG. 1) via a flange. It is necessary to connect the outflow pipe 96 so that the connection position of the outflow pipe 96 is slightly above the upper end of the dam plate 90 and to secure a height of the gas-liquid interface 84 higher than the upper end of the dam plate 90. However, when the outflow pipe 96 is provided with a valve and the outflow amount from the outflow pipe 96 is restricted by the inflow amount from the inflow pipe 94, the outflow pipe 96 may be connected to a lower position of the degassing container 88.

  According to the degassing device 14 of the vertical meandering flow system configured as described above, the reaction liquid LM mixed by the mixing device 12 flows into the degassing device 14 from the inflow pipe 94. Then, while the reaction liquid LM alternately flows in the ascending passage 86A and the descending passage 86B, the gas bubbles 98 generated as the reaction proceeds rises toward the gas-liquid interface 84 in the passage 86, and the gas-liquid interface 84 To the space 82. In this case, it is preferable that the bottom shape of the degassing container 88 in which the flow of the reaction liquid LM is reversed from the descending passage 86B to the ascending passage 86A is formed in an arc shape. Thereby, since the flow of the reaction liquid LM flows smoothly without staying at the bottom of the degassing container 88, the bubbles 98 and the metal fine particles which are reaction products do not stagnate at the bottom. As another aspect, as shown in FIG. 14, a stirrer 100 that generates a flow that prevents stagnation may be provided at the bottom of the ascending passage 86 </ b> A. If this stirrer 100 is provided, a reversal flow of a large force can be formed when the reaction liquid LM is reversed from the descending passage 86B to the ascending passage 86A, so that the bubbles 98 and the metal fine particles stay in the bottom of the degassing container 88. Can be prevented.

  Further, in order not to lengthen the length of the passage 86 unnecessarily, it is preferable that the height of the weir plate 90 is lowered as it goes from the inlet 88A to the outlet 88B of the degassing device 14. This is because, in the passage 86 formed in the degassing container 88, the gas generation amount from the reaction liquid LM is larger as it is closer to the inlet side, and the gas generation amount is smaller toward the outlet side. Therefore, it is necessary to ensure a longer passage length to the gas-liquid interface 84 on the inlet side of the passage 86, and if the height of the weir plate 90 is decreased from the inlet 88A to the outlet 88B of the degassing container 88, The passage length to the gas-liquid interface 84 can be appropriately formed according to the amount of gas generated. This prevents the length of the passage 86 from being unnecessarily lengthened, so that efficient degassing can be performed in a short time.

  As shown in FIGS. 12 and 13, the degassing device 14 is preferably provided with a pressure adjusting means 102 that adjusts the pressure of the space portion 82 that changes as bubbles are generated. In this case, when the pressure adjusting means 102 adjusts the pressure of the entire space portion 82 to be uniform, the communication hole 92 </ b> A may be formed in a portion corresponding to the space portion 82 of the baffle plate 92.

  The pressure adjusting means 102 is mainly connected to the pressure sensor 106 that measures the pressure in the space 82, the gas vent pipe 110 with a valve 108 that discharges the gas accumulated in the space 82, and the gas vent pipe 110. The pressure reducing means 112, a gas supply pipe 116 with a valve 114 for supplying an inert gas such as nitrogen gas to the space 82, and a control device 118 are configured. As the decompression means 112, a vacuum pump or an aspirator can be used. Then, the control device 118 adjusts the valves 108 and 114 of the gas vent pipe 110 and / or the gas supply pipe 116 based on the pressure value of the space part 82 measured by the pressure sensor 106, thereby adjusting the pressure of the space part 82. Adjust appropriately. That is, the pressure of the space portion 82 is adjusted so that the bubbles 98 in the reaction liquid LM flowing through the passage 86 of the degassing device 14 are easily degassed to the space portion 82 via the gas-liquid interface 84. In order to facilitate degassing, it is better to reduce the pressure in the space portion 82. However, if the pressure is reduced too much, the reaction liquid LM will boil and the flow will be disturbed. Therefore, when the pressure is reduced too much, the space 82 is adjusted by supplying an inert gas such as nitrogen gas. How much pressure is reduced depends on the amount of bubbles in the generated gas, the levitation force depending on the size of the bubbles, and the like, so the degree of pressure reduction may be adjusted while monitoring the degassing state. Therefore, it is preferable that the state where the bubbles 98 are removed from the reaction liquid LM flowing through the passage 86 can be observed, and the degassing container 88 is preferably formed of a transparent container.

  In this degassing, the generated gas is continuously degassed smoothly from the reaction liquid LM (so as not to disturb the flow of the liquid) while maintaining the pressure in the space 82 constant and accurately, and the flow of the reaction liquid LM is stabilized. It is very important to stabilize the reaction and to make it uniform.

  For this reason, it is preferable to use the valves 108 and 114 that open and close at a response speed of a level of 10 milliseconds or less, more preferably 5 milliseconds or less. Servovalves can be used as the valves 108 and 114 that open and close at a response speed of 5 milliseconds or less. As a result, when the measured value of the pressure sensor 106 fluctuates with respect to the preset pressure setting value of the space portion 82, the valves 108 and 114 open and close at a very fast opening / closing speed. I can not. Further, when the response speed of the valves 108 and 114 is 10 milliseconds or more, a resistor (not shown) that slows the gas release speed somewhere in the gas vent pipe 110 including the valve valves 108 and 114. May be provided to facilitate pressure control. As the resistor, an orifice, a filter, or the like can be preferably used.

  In addition, there are cases where the reaction is a reaction that dislikes oxygen in the air, or when the gas generated by the reaction is oxygen such as hydrogen gas, it may be dangerous. In this case, since an inert gas such as nitrogen gas can be supplied from the gas supply pipe 116, the inert gas is purged from the gas supply pipe 116 into the degassing container 88 before the reactor 10 is operated. It is preferable to replace the air in the container 88 with an inert gas.

  In the present embodiment, the communication hole 92A is formed in a portion corresponding to the space portion 82 of the baffle plate 92. However, the communication hole 92A is not formed, and each space portion 82 partitioned by the baffle plates 92 is formed. Pressure adjusting means 102 may be provided so that the pressure can be individually adjusted for each space 82. As described above, the gas generation amount from the reaction liquid LM increases as it approaches the inlet side of the degassing device 14, and the gas generation amount decreases as it approaches the outlet side. It is necessary to quickly remove the gas that has been gasified from the space 82 so that the pressure in the space 82 does not increase. Therefore, if the pressure can be adjusted for each space 82 divided by the baffle plates 92, the pressure in each space 82 is appropriately controlled according to the amount of gas generated, and the bubble 98 is generated for each space 82. Can form a pressure that is easily degassed.

  Further, in order to promote the degassing of the bubbles 98 from the reaction liquid LM, as shown in FIG. 13, temperature adjusting means for heating or cooling the reaction liquid LM flowing into the degassing device 14 in the middle of the inflow pipe 94. 120 is preferably provided. In this case, the entire degassing device 14 may be heated or cooled by embedding a heater or a cooling coil in the degassing container 88, the weir plate 90, and the baffle plate 92. To what degree the reaction liquid LM is heated or cooled, the temperature of the temperature adjusting means 120 or the like may be appropriately set while observing the state where the bubbles 98 are removed.

  Thus, by controlling the reaction temperature by heating or cooling the reaction liquid LM flowing in the degassing device 14, the reaction conditions can be made constant regardless of the air temperature or the room temperature. Can be kept constant regardless of the temperature. Therefore, accurate degassing treatment can be performed, and the degassing amount in the designed degassing device is accurately reproduced regardless of the season and room temperature, so the shape and capacity of the device are fixed. it can.

  In order to promote the degassing of the bubbles 98 from the reaction liquid LM, it is also a preferable method to provide an ultrasonic generator 122 as shown in FIG. Although the place where the ultrasonic generator 122 is provided is not particularly limited, for example, it may be provided outside the bottom of the degassing apparatus 14 as shown in FIG. The ultrasonic vibration frequency is preferably in the range of 1 kHz to 10 MHz, more preferably in the range of 1 kHz to 1 MHz, and particularly preferably in the range of 20 kHz to 200 kHz. The ultrasonic output is preferably in the range of 1 W to 10 kW, more preferably in the range of 10 W to 5 kW, and particularly preferably in the range of 100 W to 2 kW. Thus, by applying ultrasonic vibration to the reaction liquid LM, not only can the degassing of the bubbles 98 in the reaction liquid LM be promoted, but also the inner wall surface of the degassing container 88, the surface of the weir plate 90, and the baffle plate 92. It becomes easy to detach | desorb the bubble 98 adhering to the surface. In this case, it is better to apply a surface treatment that makes it difficult for the bubbles 98 to adhere to the inner wall surface of the degassing container 88, the surface of the dam plate 90, and the surface of the baffle plate 92, such as Teflon (trademark) processing.

  In order to promote the degassing of the bubbles 98 from the reaction liquid LM, as shown in FIG. 15, the width W2 of the descending passage 86B is made larger than the width W1 of the ascending passage 86A, and the passage of the ascending passage 86A. It is preferable to make the passage sectional area of the descending passage 86B larger than the sectional area. That is, since the flow direction of the reaction liquid LM and the rising direction of the bubbles 98 are the same in the ascending passage 86A, the bubbles 98 are likely to float and be separated at the gas-liquid interface 84. Since the flying direction of 98 is reversed, the bubble 98 is difficult to float and separate at the gas-liquid interface 84. Therefore, in the descending passage 86 </ b> B, the descending flow rate of the reaction liquid LM needs to be smaller than the ascending rate of the bubbles 98. In this case, since the rising speed of the bubble 98 varies depending on the bubble diameter, it is necessary to appropriately design the descending flow speed of the descending passage 86B according to the size of the bubble diameter, that is, the rising speed. In FIGS. 14 and 15, the pressure adjusting means 102 is omitted.

  In FIG. 16, the degassing device 14 is unitized into an inlet unit 124, an intermediate unit 126, and an outlet unit 128 so that the entire length of the passage 86 can be easily adjusted.

  As shown in FIG. 16, the inlet unit 124 has the above-described weir plate 90 standing inside the box body 130, an inflow pipe 94 connected to the lower portion of one side surface of the box body 124, and the lower portion of the other side surface. The outlet duct 132 is provided so as to project sideways. In the intermediate unit 126, the above-described weir plate 90 is erected inside the box body 134, and an inlet duct 136 protrudes laterally at a lower portion of one side surface of the box body 134, and an outlet duct 138 is formed at the lower portion of the other side surface. Is projected sideways. The outlet unit 128 has an inlet duct 142 projecting from the lower part of one side surface of the box 140 and an outflow pipe 96 connected to the upper part of the other side surface. Each unit 124, 126, 128 is formed with a communication hole 92A for equalizing the pressure in the space 82 described above. In addition, the inlet ducts 136 and 142 and the outlet ducts 132 and 238 in each unit 124, 126, and 128 are fitted in a watertight state.

  In order to assemble the degassing device 14 with the inlet unit 124, the intermediate unit 126, and the outlet unit 128, the outlet duct 132 of the inlet unit 124 and the inlet duct 136 of the intermediate unit 126 are fitted together, The outlet duct 138 and the inlet duct 142 of the outlet unit 128 are fitted. The side surfaces of the units 124, 126, and 128 that are brought together by this fitting become the baffle plate 92 described above. As a result, the degassing device 14 can be easily manufactured, and the length of the entire passage 86 in the degassing device 14 can be arbitrarily adjusted only by changing the number of intermediate units 126. When the communication hole 92A is formed in each unit 124, 126, 128, the pressure adjusting means described above may be provided in any unit. Further, when the communication hole 92A is not formed, the pressure adjusting means 102 for adjusting the pressure in the space 82 may be provided for each unit. In addition, various means and shapes for promoting degassing may be provided, such as providing the temperature adjusting means 120, the ultrasonic wave applying means 122, the stirrer 100, and the like, or forming the unit bottom in an arc shape.

b) Gas Permeation Method As shown in FIG. 17, the gas permeation type degassing apparatus 14 has an inflow pipe 94 connected to the upper part of one side surface of the degassing container 88 and an outflow pipe 96 at the lower part of the other side surface. Connected. In the degassing container 88, a degassing pipe 150 formed of a gas permeable member that allows gas to pass through without passing liquid is housed in an inverted S shape, and one end of the degassing pipe 150 is connected to the inflow pipe 94. The other end is connected to the outflow pipe 96. Further, a plurality of locations of the degassing pipe 150 are supported on the inner wall surface of the degassing container 88 via the holder 152.

  The most important point in manufacturing the gas permeable degassing apparatus 14 is how to use a gas permeable member having good gas permeability. For example, Gore-Tex membrane ( A membrane having a good gas permeability such as a trademark is commercially available, and such a membrane can be used. In addition, due to recent advances in micromachining technology, it has become possible to open extremely fine holes that do not allow liquids to pass through but allow gas to pass through hard resins such as metals and plastic resins. It is also possible to manufacture a gas permeable member. In any case, the gas permeable degassing device 14 may be any gas permeable member that allows only gas generated by the liquid-liquid reaction to permeate, regardless of technological progress. In this case, the entire degassing pipe 150 is not limited to being formed of a gas permeable member, and at least the upper part of the degassing pipe 150 may be formed of a gas permeable member. Thereby, in the degassing container 88, the degassing pipe 150 in which the gas-liquid interface between the liquid part 80 by the reaction liquid LM and the space part 82 in which the gas removed from the reaction liquid LM accumulates is formed by the gas permeable member. A degassing device 14 having a structure partitioned by is formed.

  According to the gas permeable degassing device 14 configured as described above, the reaction liquid LM mixed in the mixing device 12 flows into the degassing device 14 from the inflow pipe 94. Then, while the reaction liquid LM flows in the degassing pipe 150, the gas generated by the reaction rises as bubbles 98 in the reaction liquid and permeates through the degassing pipe 150 formed by the gas permeable member. Degassed to the space 82.

  In such degassing, although depending on the gas permeation performance of the gas permeable member forming the degassing pipe 150, it is preferable to provide pressure adjusting means for adjusting the pressure of the space portion 82 to depressurize the space portion 82. Since the configuration of the pressure adjusting means 102 is the same as that described in the degassing apparatus of the up and down meandering flow method, the description is omitted.

  As described above, according to the reaction apparatus 10 of the present invention, the mixing apparatus 12 and the degassing apparatus 14 are separated, and mixing is performed uniformly and efficiently without being obstructed by the gas bubbles 98 generated by the reaction. Therefore, it is possible to stabilize the reaction at the start of the reaction and in the course of the reaction, and to perform stable liquid feeding to the subsequent process.

  Further, according to the reaction apparatus 10 of the present invention, instantaneous mixing can be performed by using a high-pressure mixing system as the mixing apparatus 12, and the reaction liquid LM in which gas is generated by the start of the reaction by mixing is immediately removed. It can be sent to the gas device 14. Thereby, in the mixing apparatus 12, mixing is not disturbed by the gas bubble.

  Further, according to the reaction apparatus 10 of the present invention, the degassing apparatus 14 includes the passage 86 having the gas-liquid interface 84 between the liquid part 80 by the reaction liquid LM and the space part 82 in which the gas removed from the reaction liquid LM accumulates. Since the gas bubbles 98 in the reaction liquid formed and continuously flowing through the passage 86 are continuously removed in the space portion 82, efficient degassing utilizing the levitation force of the bubbles 98 can be performed.

  Therefore, the reaction apparatus 10 of the present invention is suitable for a reaction system in a flow system in which a reaction for generating a gas is performed in the flow of the reaction liquid LM. In particular, if the reaction apparatus 10 of the present invention is used for continuous production of magnetic particles contained in the magnetic layer of a magnetic recording medium, the reaction accompanied by gas generation can be made uniform. Moreover, it is considered that the equilibrium of the reaction proceeds toward the reaction promoting side by continuously degassing, and the reactivity is improved, so that a rapid reaction is possible, and as a result, the magnetic particles can be miniaturized. In addition, when performing liquid temperature control for degassing, the gas can be efficiently removed in the flow of continuous processing, so that the accuracy of liquid temperature control can be improved. Thereby, magnetic particles having a fine size and good monodispersibility can be produced, and a high-precision magnetic recording medium can be produced by containing the magnetic particles in the magnetic layer.

  The following operation was performed in high purity nitrogen gas.

10. Aerosol OT (manufactured by Wako Pure Chemical Industries, Ltd.) in a reducing agent aqueous solution in which 0.50 g of NaBH ₄ (manufactured by Wako Pure Chemical Industries) was dissolved in 16 ml of H ₂ O (dissolved oxygen was deoxidized to 0.1 mg / l or less). An alkane solution in which 8 g, 80 ml of decane (manufactured by Wako Pure Chemical Industries) and 2 ml of oleylamine (manufactured by Tokyo Chemical Industry) were mixed was added and mixed to prepare a reverse micelle solution of the first solution L1.

Triammonium iron oxalate (Fe (NH ₄ ) ₃ (C ₂ O ₄ ) ₃ ) (manufactured by Wako Pure Chemical Industries) 0.60 g and potassium chloroplatinate (K ₂ PtCl ₄ ) (manufactured by Wako Pure Chemical Industries) 0.50 g Is added to an aqueous solution of metal salt dissolved in 8 ml of H ₂ O (dissolved oxygen is deoxidized to 0.1 mg / l or less), 7.0 g of aerosol OT (manufactured by Wako Pure Chemical Industries) and decane (manufactured by Wako Pure Chemical Industries). An alkane solution mixed with 40 ml was added and mixed to prepare a reverse micelle solution of the second solution L2.

  In the method for producing fine metal particles according to the conventional method, the above two reverse micelle solutions (L1, L2) were stirred and mixed for 10 minutes in a single tank and reacted. Thus, the obtained metal fine particles are referred to as a conventional method sample.

  In contrast, in the reaction apparatus 10 of the present invention, the reverse micelle solution (L1) and the reverse micelle solution (L2) were instantaneously mixed using the mixing apparatus 12 of FIG. Simultaneously with the completion of the mixing, the reaction solution LM was taken out from the mixing device 12, and after 10 minutes, the reaction solution LM was recovered in the recovery tank 23 while removing the gas with the up and down meandering type degassing device 14 of FIG. Thus, the obtained metal fine particles are referred to as a sample according to the present invention.

The following operations are the same for both the conventional method and the method of the present invention. That is, both the conventional method sample and the method sample of the present invention were then aged for 60 minutes by raising the temperature to 50 ° C. while stirring with a magnetic stirrer. Next, 2 ml of oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, mixed and cooled to room temperature, and then taken out into the atmosphere. In order to destroy the reverse micelle, a mixed solution of 100 ml of H ₂ O (dissolved oxygen was deoxidized to 0.1 mg / l or less) and 100 ml of methanol was added to separate into an aqueous phase and an oil phase. A state in which the metal nanoparticles were dispersed on the oil phase side was obtained. The oil phase side was washed 5 times with a mixed solution of 600 ml of H ₂ O (dissolved oxygen was deoxidized to 0.1 mg / l or less) and 200 ml of methanol. Thereafter, 1100 ml of methanol was added to cause flocculation of the metal nanoparticles and sedimentation. After removing the supernatant, 20 ml of heptane (manufactured by Wako Pure Chemical Industries, Ltd.) was added and redispersed, and then 100 ml of methanol was added to precipitate the metal nanoparticles. This treatment is repeated three times, and finally 5 ml of octane (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a FePt metal nanoparticle dispersion with a mass ratio of water to surfactant (water / surfactant) of 2. Obtained.

  The yield, composition, volume average particle size and particle size distribution (coefficient of variation), and coercive force of the obtained conventional metal nanoparticles and the metal nanoparticles of the present invention were measured. The composition and yield were measured by ICP spectroscopic analysis (inductively coupled high-frequency plasma spectroscopic analysis), and the volume, average particle size, and particle size distribution were determined by statistical processing by measuring particles taken by TEM. The coercive force was measured using a high sensitivity magnetization vector measuring machine manufactured by Toei Kogyo Co., Ltd. and a DATA processing apparatus manufactured by the same company under the condition of an applied magnetic field of 790 kA / m (10 kOe). The metal nanoparticles for measurement were measured using metal nanoparticles collected from the prepared metal nanoparticle dispersion, sufficiently dried, and heated in an electric furnace at 550 ° C. for 30 minutes.

  Table 1 shows the measurement results of the metal nanoparticles of the conventional method and the metal nanoparticles of the present invention in Example 1.

表１の結果から分かるように、本発明法の金属ナノ粒子は、従来法の金属ナノ粒子に比べて、微小サイズで且つ単分散性に優れた粒子が得られた。また、本発明法は従来法に比べて収率が増加すると共に組成もＰｔの含有率が増加した。

As can be seen from the results in Table 1, the metal nanoparticles of the present invention were finer in size and monodisperse than the conventional metal nanoparticles. Further, the method of the present invention increased the yield and the content of Pt in the composition as compared with the conventional method.

The conceptual diagram which comprised the apparatus for continuously manufacturing a metal microparticle using the reaction apparatus of this invention. Sectional drawing which shows the mixing apparatus of the one jet type high pressure mixing system in the reaction apparatus of this invention Explanatory drawing explaining the mixing theory of the one-jet type high-pressure mixing method Explanatory drawing explaining the shape of the 1st nozzle of the mixing apparatus of a one jet type high pressure mixing system Explanatory drawing explaining another shape of the 1st nozzle Explanatory drawing explaining further another shape of the 1st nozzle Explanatory drawing explaining the other shape of the 1st nozzle Sectional view showing a T-shaped high-pressure mixing device Sectional view showing a Y-shaped high pressure mixing system Sectional view showing a two-jet opposed high-pressure mixing device Explanatory drawing explaining the mixing theory of the two-jet opposed high-pressure mixing method The perspective view which shows the degassing apparatus of the up-and-down meander flow system in the reaction apparatus of this invention Sectional drawing which shows the concept of the degassing apparatus of an up-and-down meander flow Sectional drawing of the aspect which provided the stirrer in the bottom part of the degassing apparatus of an up-and-down meandering type Cross-sectional view of the width of the ascending and descending passages of the degassing device of the up and down meandering flow system Upper / lower meandering flow type degassing unit as an exploded view Sectional view showing the concept of a gas permeation type degassing device

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Reaction apparatus, 12 ... Mixing apparatus, 14 ... Degassing apparatus, 16, 18 ... Preparation tank, 20 ... Heating jacket, 22, 24 ... Supply piping, 26, 28 ... Supply pump, 30, 32 ... Pipe, 34 ... Product tank, 36 ... heating / cooling jacket, 38 ... mixing chamber, 40 ... mixer, 42 ... first conduit, 44 ... discharge tube, 46 ... second conduit, 48 ... first orifice, 50 ... second , 52 ... first nozzle, 54 ... second nozzle, 56 ... jacket, 58 ... orifil material, 60 ... third orifice, 62 ... first addition piping, 64 ... mixing field, 66 ... second 68 ... discharge pipe, 70 ... jacket, 80 ... liquid part, 82 ... space part, 84 ... gas-liquid interface, 86 ... passage, 86A ... ascending passage, 86B ... descending passage, 88 ... degassing vessel, 90 ... weir plate, 92 ... baffle plate, 92A Communicating hole, 94 ... Inflow pipe, 96 ... Outflow pipe, 98 ... Bubble, 100 ... Stirrer, 102 ... Pressure adjusting means, 106 ... Pressure sensor, 108 ... Valve, 110 ... Degassing pipe, 112 ... Pressure reducing means, 114 ... Valve 116 ... Gas supply pipe, 118 ... Control device, 120 ... Temperature adjusting means, 122 ... Ultrasonic generator, 124 ... Inlet unit, 126 ... Intermediate unit, 128 ... Outlet unit, 130, 134, 140 ... Box, 132 DESCRIPTION OF SYMBOLS 138 ... Outlet duct, 136, 142 ... Inlet duct, 150 ... Degassing pipe, L1 ... 1st solution, L2 ... 2nd solution, LM ... Reaction liquid

Claims (26)

In the reaction method of the reaction system in which gas is generated with the reaction,
Separating a sealed mixing unit that starts reaction by mixing a plurality of liquids and a degassing unit having a gas-liquid interface for removing gas bubbles generated from the mixed reaction solution from the reaction solution A reaction method comprising feeding the reaction solution mixed in the mixing unit to the degassing unit.   The reaction method according to claim 1, wherein instantaneous mixing is performed in the mixing unit.   The degassing part is a passage that forms the gas-liquid interface by a liquid part by the reaction liquid and a space part in which the gas removed from the reaction liquid is accumulated, and bubbles of gas in the reaction liquid flowing through the passage The reaction method according to claim 1 or 2, characterized in that is removed in the space.   The reaction method according to claim 3, wherein the pressure in the space is reduced.   The passage has an ascending passage and a descending passage through which the reaction solution continuously flows, and forms the gas-liquid interface at a portion where the flow is reversed from the ascending passage to the descending passage. Reaction method 3 or 4.   The reaction method according to claim 3, wherein the reaction liquid flows through a passage in which the ascending passage and the descending passage are configured in multiple stages.   The reaction method according to any one of claims 1 to 6, wherein the reaction temperature is controlled by heating or cooling the reaction liquid flowing through the degassing section.   The reaction method according to claim 1, wherein an ultrasonic wave is applied to the reaction liquid flowing through the degassing unit.   The reaction method according to any one of claims 5 to 8, wherein the flow rate of the reaction liquid flowing through the descending passage is slower than the rising speed of the bubbles.   The reaction method according to claim 1, wherein the inside of the degassing part can be seen through. In a reaction system reactor that generates gas with the reaction,
A closed mixing unit that starts reaction by mixing a plurality of liquids;
A degassing section provided separately from the mixing section in an apparatus, and having a gas-liquid interface for removing gas bubbles generated from the reaction liquid mixed in the mixing section from the reaction liquid. A reactor characterized by that.   The mixing unit is a high-pressure mixing device that supplies at least one liquid of the plurality of liquids to a mixing chamber having a residence time of 5 seconds or less by a high-pressure jet flow of 1 MPa or more and instantaneously mixes with other liquids. 12. A reactor according to claim 11 characterized in that The degassing part is a passage that forms the gas-liquid interface by a liquid part by the reaction liquid and a space part in which the gas removed from the reaction liquid is accumulated,
A degassing vessel having an inlet and an outlet for the reaction solution;
A plurality of dam plates standing from the bottom of the degassing vessel and having an upper end located below the gas-liquid interface;
Provided between the barrier plates, the upper end is located above the gas-liquid interface and the lower end is composed of a baffle plate spaced from the bottom of the degassing container,
An ascending passage and a descending passage through which the reaction solution continuously flows are formed in the degassing container, and the gas-liquid interface is formed at a portion where the flow is reversed from the ascending passage to the descending passage. The reaction apparatus according to claim 11 or 12, characterized in that:   The reactor according to claim 13, wherein the space portion is not partitioned by the baffle plate.   The reactor according to claim 13 or 14, wherein the height of the weir plate is low from the entrance to the exit of the degassing vessel.   The reaction apparatus according to any one of claims 13 to 15, further comprising pressure adjusting means for adjusting the pressure in the space.   The reaction apparatus according to any one of claims 11 to 16, wherein the degassing unit is provided with temperature adjusting means for controlling the reaction temperature by heating or cooling the reaction solution.   The reaction apparatus according to any one of claims 11 to 17, wherein the degassing unit is provided with an ultrasonic wave applying means for applying an ultrasonic wave to the reaction liquid.   The reactor according to any one of claims 13 to 18, wherein a stirrer for forming a flow for preventing stagnation is provided at a bottom portion of the rising passage formed in the degassing vessel.   The reactor according to any one of claims 13 to 19, wherein a cross-sectional area of the descending passage is different from that of the ascending passage.   21. The surface treatment according to claim 13, wherein the inner surface of the degassing vessel, the surface of the dam plate, and the surface of the baffle plate are subjected to surface treatment that prevents the gas bubbles from adhering. Reactor.   The reactor according to any one of claims 13 to 21, wherein a bottom shape of a degassing vessel in which the flow of the reaction liquid is reversed from the descending passage to the ascending passage is formed in an arc shape.   23. The reaction apparatus according to claim 13, wherein the reaction by the plurality of liquids is a reaction for generating magnetic particles.   Magnetic particles produced using the reaction method according to any one of claims 1 to 10.   A magnetic particle produced by using any one of the reactors according to claim 11.   A magnetic recording medium comprising the magnetic particles according to claim 24 or 25 in a magnetic layer.

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